CN105814094B - Light wet-cured type resin combination, electronic component-use bonding agent and display element bonding agent - Google Patents
Light wet-cured type resin combination, electronic component-use bonding agent and display element bonding agent Download PDFInfo
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- CN105814094B CN105814094B CN201580002997.7A CN201580002997A CN105814094B CN 105814094 B CN105814094 B CN 105814094B CN 201580002997 A CN201580002997 A CN 201580002997A CN 105814094 B CN105814094 B CN 105814094B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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Abstract
The purpose of the present invention is to provide the light wet-cured type resin combinations excellent in reliability under cementability and hot and humid environment.In addition, the object of the invention is also to provide use electronic component-use bonding agent and display element bonding agent made of the light wet-cured type resin combination.The present invention is a kind of smooth wet-cured type resin combination, it contains free-radical polymerised compound, wet-cured type polyurethane resin and optical free radical polymerization initiator, and above-mentioned wet-cured type polyurethane resin contains the compound with group and isocyanate group shown in urethane bond, following formula (1).In formula (1), R1And R2For hydrogen, the alkyl or aryl of carbon number 1~5, R1And R2It can be identical or different respectively.X is 0~2.-Si(R1)x(OR2)3‑x(1)。
Description
Technical field
The present invention relates to the light wet-cured type resin combinations excellent in reliability under cementability and hot and humid environment.Separately
Outside, viscous the invention further relates to using electronic component-use bonding agent made of the light wet-cured type resin combination and display element to use
Connect agent.
Background technique
In recent years, as the display element with slim, lightweight, low power consumption, liquid crystal display member is utilized extensively
Part, organic EL display element etc..In these display elements, usually in the sealing of liquid crystal or luminescent layer, substrate, optical film, guarantor
Photocurable resin composition is used in bonding of cuticula, various components etc..
But in the modern times that the various mobile devices with display element such as mobile phone, portable game are popularized, display element
Miniaturization be the technical issues of needing most solution, as the method for miniaturization, implementation is to make image displaying part narrow edge
(hereinafter, also referred to as narrow edge designs).However, it is solid to apply lighting in the part that light does not substantially arrive at sometimes in narrow edge design
Change type resin combination, the solidification that as a result there is the photocurable resin composition for being coated on the part that light does not reach are insufficient
Problem.Therefore, even if using photo-thermal curing type resin combination as also capable of sufficiently solidifying when being coated on part that light do not reach
Resin combination, and and with photocuring and heat cure, but exist and bad shadow generated to element etc. due to the heating under high temperature
Loud risk.
Make the cured method of resin combination as without the heating under high temperature, Patent Document 1 discloses make
With the carbamate prepolymer contained at least one isocyanate group and at least one (methyl) acryloyl group in molecule
Light wet-cured type resin combination and and with the method for photocuring and moisturecuring.However, using light disclosed in patent document 1
In the case where wet-cured type resin combination, under the cementability, hot and humid environment when being sometimes bonded the adherends such as substrate
Reliability (especially creep resistant) is insufficient.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2008-274131 bulletin
Summary of the invention
Problems to be solved by the invention
The purpose of the present invention is to provide the light wet-cured type trees excellent in reliability under cementability and hot and humid environment
Oil/fat composition.In addition, the object of the invention is also to provide use electronic component made of the light wet-cured type resin combination
With bonding agent and display element bonding agent.
The means used to solve the problem
The present invention is a kind of smooth wet-cured type resin combination, poly- containing free-radical polymerised compound, wet-cured type
Urethane resin and optical free radical polymerization initiator, above-mentioned wet-cured type polyurethane resin contain with urethane bond, following
The compound of group and isocyanate group shown in formula (1).
[changing 1]
-Si(R1)x(OR2)3-x (1)
In formula (1), R1And R2For hydrogen, the alkyl or aryl of carbon number 1~5, R1And R2It can be identical or different respectively.X is 0
~2.
Hereinafter, the present invention is described in detail.
The inventors of the present invention, which have found surprisingly that, is containing free-radical polymerised compound, wet-cured type polyurethane resin and light
In the light wet-cured type resin combination of radical polymerization initiator, by using the compound with particular functional group as wet
Curable polyurethane resin, the light wet-cured type resin group excellent in reliability under available cementability and hot and humid environment
Close object.So that completing the present invention.
Light wet-cured type resin combination of the invention contains wet-cured type polyurethane resin.Above-mentioned wet-cured type polyurethane
The isocyanate group of the intramolecular of resin solidifies in air or solidifies with the reaction of moisture in adherend.
Above-mentioned wet-cured type polyurethane resin contains with group and isocyanide shown in urethane bond, above-mentioned formula (1)
The compound of perester radical (hereinafter, also referred to as " polyurethane resin containing Organosilyl ").By containing organic first containing above-mentioned
The polyurethane resin of silylation is as wet-cured type polyurethane resin, so that light wet-cured type resin combination of the invention is viscous
Reliability under connecing property and hot and humid environment becomes excellent.
The above-mentioned polyurethane resin containing Organosilyl has group shown in above-mentioned formula (1).
In above-mentioned formula (1), from the excellent effect aspect for improving the reliability under cementability and hot and humid environment,
R1And R2The preferably alkyl of carbon number 1~5, more preferably methyl, ethyl.
In addition, in R1And R2In the case where for aryl, as the aryl, it can be mentioned, for example phenyl, naphthalene, 2- aminomethyl phenyls
Deng.
It should be noted that the x in above-mentioned formula (1) refers to the case where being 0: silicon atom does not have and R1Shown in atom or base
Group bonding and with 3-OR2The case where base is bonded.
The above-mentioned polyurethane resin containing Organosilyl has isocyanate group.
The above-mentioned polyurethane resin containing Organosilyl can only have 1 isocyanate group in 1 molecule, can also be with
With 2 or more isocyanate group.
The above-mentioned polyurethane resin containing Organosilyl preferably respectively end have above-mentioned formula (1) shown in group and
Above-mentioned isocyanate group.
The above-mentioned polyurethane resin containing Organosilyl can be by making with urethane bond and isocyanate group
Compound, react and obtains with the compound with group shown in reactive functional groups and formula (1), it is described with amino first
Acid esters key and the compound of isocyanate group are by making polyol compound and 1 molecule in 1 molecule with 2 or more hydroxyls
In the polyisocyanate compounds reaction with 2 or more isocyanate group obtain.It should be noted that above-mentioned " reactivity
Functional group " is the group for referring to be reacted with the above-mentioned compound with urethane bond and isocyanate group.
Above-mentioned polyol compound reacts usually in above-mentioned polyol compound with above-mentioned polyisocyanate compounds
Hydroxyl (OH) and above-mentioned polyisocyanate compounds in isocyanate group (NCO) molar ratio be [NCO]/[OH]=2.0
It is carried out in the range of~2.5.
As above-mentioned polyol compound, the commonly used well known polyalcohol in the manufacture of polyurethane can be used
Compound, it can be mentioned, for example polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyols etc..These are more
First alcoholic compound may be used singly or in combination of two or more.
As above-mentioned polyester polyol, it can be mentioned, for example: the polyester as obtained from the reacting of polybasic carboxylic acid and polyalcohol
Polyalcohol makes poly- 6-caprolactone polyalcohol etc. obtained from 6-caprolactone ring-opening polymerisation.
As the above-mentioned polybasic carboxylic acid for the raw material for becoming above-mentioned polyester polyol, it can be mentioned, for example terephthalic acid (TPA)s, isophthalic
Dioctyl phthalate, 1,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,
Decanedioic acid, decamethylene dioctyl phthalate, ten dimethylene dioctyl phthalate etc..
As the above-mentioned polyalcohol for the raw material for becoming above-mentioned polyester polyol, it can be mentioned, for example ethylene glycol, propylene glycol, 1,
3-propanediol, 1,4- butanediol, neopentyl glycol, 1,5- pentanediol, 1,6-HD, diethylene glycol, cyclohexanediol etc..
As above-mentioned polyether polyol, it can be mentioned, for example ethylene glycol, propylene glycol, tetrahydrofuran, 3- methyltetrahydrofurans
The random copolymer of ring opening polymerizable compound and these compounds or derivatives thereof or the polyoxy of block copolymer, bisphenol type
Change alkene modifier etc..
The polyoxyalkylene-modified object of above-mentioned bisphenol type is the active hydrogen moieties and alkylene oxide (example for making bisphenol type molecular skeleton
Such as ethylene oxide, propylene oxide, epoxy butane, epoxy iso-butane etc.) carry out polyether polyol obtained by addition reaction, Ke Yiwei
Random copolymer, or block copolymer.About the polyoxyalkylene-modified object of above-mentioned bisphenol type, preferably in bisphenol type molecule
The one kind or two or more alkylene oxide of two terminal additions of skeleton.It as bisphenol type, is not particularly limited, A type, F type, S can be enumerated
Type etc., preferably bisphenol A-type.
As above-mentioned polyalkylene polyol, it can be mentioned, for example polybutadiene polyols, hydrogenated butadiene polymer polyalcohol, hydrogen
Change polyisoprene polyol etc..
As above-mentioned polycarbonate polyol, it can be mentioned, for example polyhexamethylene carbonate polyol, polycyclic hexane two are sub-
Methyl carbonic acid ester polyol etc..
As above-mentioned polyisocyanate compounds, it can be mentioned, for example methyl diphenylene diisocyanates, diphenyl methane two
The liquid modifier of isocyanates, polymeric MDI (methane diisocyanate), toluene di-isocyanate(TDI), naphthalene -1,5- diisocyanate
Ester etc..Wherein, from vapour pressure or toxicity it is low in terms of, ease of handling aspect, preferably diphenylmethane diisocyanate
Ester and its modifier.Above-mentioned polyisocyanate compounds may be used singly or in combination of two or more.
As the above-mentioned compound with group shown in reactive functional groups and formula (1), it can be mentioned, for example 3- sulfydryls third
Base trimethoxy silane, 3- Mercaptopropyltriethoxysilane, 3- mercapto propyl methyl dimethoxy silane, 3- sulfydryl third
Ylmethyl diethoxy silane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group triethoxysilicane
Alkane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyl diethoxy silane, 2- (3,
4- epoxycyclohexyl) ethyl trimethoxy silane, 3- glycidoxypropyl diethoxy silane, 3- aminopropyl
Trimethoxy silane, 3-aminopropyltriethoxysilane, 3- (2- amino-ethyl) TSL 8330,3-
(2- amino-ethyl) aminopropyltriethoxywerene werene, 3- (2- amino-ethyl) aminopropylmethyldimethoxysilane,
3- (methyl) acryloyloxypropyltrimethoxysilane, 3- (methyl) acryloxypropyl triethoxysilane, 3-
(methyl) acryloxypropyl dimethoxysilane, 3- (methyl) acryloyloxy propyl methyl diethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, 3- isocyanate propyl trimethoxysilane etc..Wherein, from anti-
From the perspective of answering property, preferably there is compound of the mercapto as reactive functional groups.
It should be noted that in the present specification, above-mentioned " (methyl) acryloyl group " refers to acryloyl group or metering system
Acyl group.
For the content of the above-mentioned polyurethane resin containing Organosilyl, relative to free-radical polymerised compound with
Total 100 parts by weight of wet-cured type polyurethane resin, preferred lower limit is 1 parts by weight, the preferred upper limit is 50 parts by weight.If
The content of the above-mentioned polyurethane resin containing Organosilyl is then unable to give full play raising cementability less than 1 parts by weight sometimes
And the effect of the reliability under hot and humid environment.If the content of the above-mentioned polyurethane resin containing Organosilyl is more than 50 weights
Amount hinders the reaction of wet-cured type polyurethane resin sometimes, reduces the elasticity modulus of solidfied material, be unable to ensure sufficient bonding
Power.The preferred lower limit of the content of the above-mentioned polyurethane resin containing Organosilyl is 2 parts by weight, the preferred upper limit is
30 parts by weight, further preferred lower limit are 5 parts by weight, the further preferred upper limit is 25 parts by weight.
Light wet-cured type resin combination of the invention is preferably also containing in addition to the polyurethane resin containing Organosilyl
Other wet-cured type polyurethane resins in addition.By containing other other than the polyurethane resin containing Organosilyl
Wet-cured type polyurethane resin, to be easily adjusted curability.
As above-mentioned other wet-cured type polyurethane resins, it is preferable to use above-mentioned have urethane bond and isocyanic acid
The compound of ester group.
Hereinafter, for the wet-cured type polyurethane resin entirety institute comprising the above-mentioned polyurethane resin containing Organosilyl
For common item, only handled as " wet-cured type polyurethane resin ".
Above-mentioned wet-cured type polyurethane resin is preferably using the polyol compound with structure shown in following formula (2)
Obtained from polyurethane resin.By using the polyol compound with structure shown in following formula (2), so as to obtain
Composition or the soft and good solidfied material of draftability excellent in adhesion, it is compatible with above-mentioned free-radical polymerised compound
Property is excellent.In addition, above-mentioned wet-cured type polyurethane resin preferably has branch.
Wherein, it is preferable to use comprising propylene glycol, tetrahydrofuran (THF) compound ring opening polymerizable compound, have methyl
The polyurethane resin of the polyether polyol of the ring opening polymerizable compound of the tetrahydrofuran-compound of equal substituent groups.
[changing 2]
In formula (2), R indicates hydrogen, methyl or ethyl, the integer that n is 1~10, the integer that L is 0~5, m be 1~500 it is whole
Number.It is preferably 0~4, m is preferably 50~200 that n, which is preferably 1~5, L,.
It should be noted that L refers to the directly oxygen-bonded situation of the carbon being bonded with R the case where being 0.
In addition, above-mentioned wet-cured type polyurethane resin can have radically polymerizable group group.
As the radically polymerizable group group that above-mentioned wet-cured type polyurethane resin can have, preferably have unsaturated double
The group of key, especially from reactive aspect, more preferable (methyl) acryloyl group.
It should be noted that the wet-cured type polyurethane resin with radically polymerizable group group is as the poly- ammonia of wet-cured type
Ester resin is handled, and is not comprised in free-radical polymerised compound.
The preferred lower limit of the weight average molecular weight of above-mentioned wet-cured type polyurethane resin is 800, the preferred upper limit is 10,000.
If the weight average molecular weight of above-mentioned wet-cured type polyurethane resin is less than 800, crosslink density is got higher, and damages flexibility sometimes.If
The weight average molecular weight of above-mentioned wet-cured type polyurethane resin is more than 10,000, then sometimes resulting smooth wet-cured type resin combination at
For the composition of coating difference.The preferred lower limit of the weight average molecular weight of above-mentioned wet-cured type polyurethane resin is 2000, more
The preferred upper limit is 8000, further preferred lower limit is 2500, the further preferred upper limit is 6000.
It should be noted that the above-mentioned weight average molecular weight in this specification is to be carried out using gel permeation chromatography (GPC)
Measure and changed using polystyrene and the value that acquires.When as the weight average molecular weight to be converted using GPC measurement with polystyrene
Column, it can be mentioned, for example Shodex LF-804 (Showa electrician corporation) etc..In addition, as the solvent used in GPC, it can
Enumerate tetrahydrofuran etc..
For the content of above-mentioned wet-cured type polyurethane resin, relative to above-mentioned free-radical polymerised compound with it is above-mentioned
Total 100 parts by weight of wet-cured type polyurethane resin, preferred lower limit is 20 parts by weight, the preferred upper limit is 90 parts by weight.
If the content of above-mentioned wet-cured type polyurethane resin less than 20 parts by weight, sometimes resulting smooth wet-cured type resin combination at
For the composition of moisture curable difference.If the content of above-mentioned wet-cured type polyurethane resin is more than 90 parts by weight, sometimes resulting
Light wet-cured type resin combination becomes the composition of photo-curable difference.The content of above-mentioned wet-cured type polyurethane resin it is more excellent
The lower limit of choosing is 30 parts by weight, the preferred upper limit is 75 parts by weight, and further preferred lower limit is 41 parts by weight, further excellent
The upper limit of choosing is 70 parts by weight.
Light wet-cured type resin combination of the invention contains free-radical polymerised compound.
As above-mentioned free-radical polymerised compound, as long as being for the free-radical polymerised compound with optical polymerism
Can, as long as being not particularly limited for the compound with radically polymerizable group group in molecule, preferably there is unsaturated double-bond
As the compound of radically polymerizable group group, especially from reactive aspect, preferably with (methyl) acryloyl group
Compound (hereinafter, also referred to as " (methyl) acrylic compounds ").
It should be noted that in the present specification, above-mentioned " (methyl) acrylic compounds " refer to acrylic compounds or metering system
Acids.
As above-mentioned (methyl) acrylic compounds, it can be mentioned, for example make (methyl) acrylic acid and the chemical combination with hydroxyl
Object reaction obtained by ester compounds, react (methyl) acrylic acid with epoxide obtained by epoxy (methyl) acrylate,
Carbamate (methyl) propylene obtained by reacting isocyanate compound with (methyl) acrylic acid derivative with hydroxyl
Acid esters etc..
It should be noted that in the present specification, above-mentioned " (methyl) acrylate " refers to acrylate or metering system
Acid esters.In addition, becoming the isocyanate group of the isocyanate compound of the raw material of above-mentioned carbamate (methyl) acrylate
It is all used to form urethane bond, above-mentioned carbamate (methyl) acrylate does not have residual isocyanate base.
As the ester compounds of the simple function in above-mentioned ester compounds, it can be mentioned, for example (methyl) acrylic acid 2- hydroxyl second
Ester, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxybutyl,
(methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate,
(methyl) stearyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- first
Oxygroup ethyl ester, methoxy ethyl glycol (methyl) acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid four
Hydrogen chaff ester, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) phenoxyethyl acrylate, benzene oxygen
Base diethylene glycol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) third
Olefin(e) acid ester, 2,2,2- trifluoroethyl (methyl) acrylate, tetra- fluoropropyl of 2,2,3,3- (methyl) acrylate, (methyl) third
Olefin(e) acid 1H, 1H, 5H- octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) acrylic acid second
Ester, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- ethyl
Own ester, (methyl) n-octyl, the different nonyl ester of (methyl) acrylic acid, the different myristin of (methyl) acrylic acid, (methyl) propylene
Sour 2- butoxyethyl, (methyl) acrylic acid 2- phenoxy ethyl, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) acrylic acid
Isodecyl ester, (methyl) diethylaminoethyl acrylate, (methyl) dimethylaminoethyl acrylate, 2- (methyl) acryloxy
Ethylsuccinic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl 2- hydroxyl
Base propyl phthalic acid ester, (methyl) glycidyl acrylate, 2- (methyl) acryloyl-oxyethyl phosphate, N- third
The phthalimides esters of acrylic acid such as alkene trimethylammonium hexahydrophthalic phthalimide, various acid imide acrylate
Deng.
In addition, the ester compounds as 2 functions in above-mentioned ester compounds, it can be mentioned, for example two (first of 1,4-butanediol
Base) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonyl two
Alcohol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, 2- normal-butyl -2- ethyl -1,3- the third two
Alcohol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol
(methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, two (first of tetraethylene glycol
Base) acrylate, polyethylene glycol two (methyl) acrylate, propylene oxide addition bisphenol-A two (methyl) acrylate, epoxy second
Alkane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, two (methyl) acrylic acid
Dihydroxymethyl bicyclopentadiene ester, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ring
Oxidative ethane is modified isocyanuric acid two (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- (methyl) acryloxy third
Ester, carbonate diol two (methyl) acrylate, polyetherdiol two (methyl) acrylate, polyester-diol two (methyl) acrylic acid
Ester, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc..
In addition, it can be mentioned, for example three (first of pentaerythrite as ester compounds more than 3 functions in above-mentioned ester compounds
Base) acrylate, trimethylolpropane tris (methyl) acrylate, propylene oxide addition trimethylolpropane tris (methyl) propylene
Acid esters, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl)
Acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons
Penta tetrol six (methyl) acrylate, two (trihydroxy methyl) propane four (methyl) acrylate, pentaerythrite four (methyl) propylene
Acid esters, glycerine three (methyl) acrylate, propylene oxide addition glycerine three (methyl) acrylate, three (methyl) acryloyls
Oxygroup ethyl phosphonic acid ester etc..
As above-mentioned epoxy (methyl) acrylate, it can be mentioned, for example make epoxide with (methyl) acrylic acid according to normal
Epoxy (methyl) acrylate etc. obtained by rule method is reacted in the presence of basic catalyst.
As the epoxide become for synthesizing the raw material of above-mentioned epoxy (methyl) acrylate, it can be mentioned, for example double
Phenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bisphenol type epoxy resin,
A Hydrogenated Bisphenol A type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy
Resin, thioether-type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol
Phenol aldehyde type epoxy resin, o-cresol phenol aldehyde type epoxy resin, dicyclopentadiene phenolic type epoxy resin, biphenyl phenolic epoxy tree
Rouge, naphthol novolac type epoxy resin, glycidyl group amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type
Epoxy resin, glycidyl ester compounds, bisphenol A-type episulfide resin etc..
As the commercially available product in above-mentioned bisphenol A type epoxy resin, it can be mentioned, for example: Epikote 828EL, Epikote
1001, Epikote 1004 (being Mitsubishi Chemical Ind's system)；Epiclon 850-S (DIC corporation) etc..
As the commercially available product in above-mentioned bisphenol f type epoxy resin, it can be mentioned, for example Epikote 806, Epikote 4004
(being Mitsubishi Chemical Ind's system) etc..
As the commercially available product in above-mentioned bisphenol-s epoxy resin, it can be mentioned, for example Epiclon EXA1514 (DIC companies
System) etc..
As the commercially available product in above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, it can be mentioned, for example RE-810NM
(Japanese chemical drug corporation) etc..
As the commercially available product in above-mentioned A Hydrogenated Bisphenol A type epoxy resin, it can be mentioned, for example Epiclon EXA7015, (DIC is public
Department's system) etc..
As the commercially available product in above-mentioned propylene oxide addition bisphenol A type epoxy resin, it can be mentioned, for example EP-4000S
(ADEKA corporation) etc..
As the commercially available product in above-mentioned resorcinol type epoxy resin, it can be mentioned, for example EX-201 (Nagase chemteX
Corporation) etc..
As the commercially available product in above-mentioned biphenyl type epoxy resin, it can be mentioned, for example Epikote YX-4000H (Mitsubishi Chemicals
Corporation) etc..
As the commercially available product in above-mentioned thioether-type epoxy resin, it can be mentioned, for example YSLV-50TE, (aurification is lived by Nippon Steel
Corporation) etc..
As the commercially available product in above-mentioned diphenyl ether type epoxy, it can be mentioned, for example YSLV-80DE, (gold is lived by Nippon Steel
Chemical company's system) etc..
As the commercially available product in above-mentioned dicyclopentadiene-type epoxy resin, it can be mentioned, for example EP-4088S (ADEKA companies
System) etc..
As the commercially available product in above-mentioned naphthalene type epoxy resin, it can be mentioned, for example Epiclon HP4032, Epiclon EXA-
4700 (being DIC corporation) etc..
As the commercially available product in above-mentioned phenol novolak type epoxy, it can be mentioned, for example Epiclon N-770 (DIC companies
System) etc..
As the commercially available product in above-mentioned o-cresol phenol aldehyde type epoxy resin, it can be mentioned, for example Epiclon N-670-
EXP-S (DIC corporation) etc..
As the commercially available product in above-mentioned dicyclopentadiene phenolic type epoxy resin, it can be mentioned, for example Epiclon HP7200
(DIC corporation) etc..
As the commercially available product in above-mentioned biphenyl phenol aldehyde type epoxy resin, it can be mentioned, for example NC-3000P (Japanese chemical drug companies
System) etc..
As the commercially available product in above-mentioned naphthol novolac type epoxy resin, it can be mentioned, for example ESN-165S, (aurification is lived by Nippon Steel
Learn corporation) etc..
As the commercially available product in above-mentioned glycidyl group amine type epoxy resin, it can be mentioned, for example 630 (Mitsubishis of Epikote
Learn corporation), Epiclon 430 (DIC corporation), TETRAD-X (gas chemical company of Mitsubishi system) etc..
As the commercially available product in abovementioned alkyl polyol type epoxy resin, it can be mentioned, for example ZX-1542, (gold is lived by Nippon Steel
Chemical company's system), Epiclon 726 (DIC corporation), Epolight 80MFA (chemical company of common prosperity society system), Denacol
EX-611 (Nagase chemteX corporation) etc..
Commercially available product in modified version epoxy resin as above-mentioned rubber (is new it can be mentioned, for example YR-450, YR-207
Day iron lives aurification corporation), Epolead PB (Daicel chemical industrial company system) etc..
As the commercially available product in above-mentioned glycidyl ester compounds, it can be mentioned, for example Denacol EX-147 (Nagase
ChemteX corporation) etc..
As the commercially available product in above-mentioned bisphenol A-type episulfide resin, it can be mentioned, for example Epikote YL-7000 (Mitsubishis
Chemical company's system) etc..
As other commercially available products in above-mentioned epoxy resin, it can be mentioned, for example YDC-1312, YSLV-80XY, YSLV-
90CR (being that aurification corporation is lived by Nippon Steel), XAC4151 (Asahi Kasei Corporation's system), Epikote 1031, Epikote
1032 (being Mitsubishi Chemical Ind's system), EXA-7120 (DIC corporation), TEPIC (Nissan Chemical corporation) etc..
As the commercially available product in above-mentioned epoxy (methyl) acrylate, it can be mentioned, for example EBECRYL 860, EBECRYL
3200、EBECRYL 3201、EBECRYL 3412、EBECRYL 3600、EBECRYL 3700、EBECRYL 3701、EBECRYL
3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX 63182 (are Daicel-
Allnex corporation), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (be in new
Chemical industrial company of village system), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy
Ester 200PA、Epoxy Ester 80MFA、Epoxy Ester 3002M、Epoxy Ester 3002A、Epoxy Ester
1600A、Epoxy Ester 3000M、Epoxy Ester 3000A、Epoxy Ester 200EA、Epoxy Ester400EA
(being chemical company of common prosperity society system), Denacol Acrylate DA-141, Denacol Acrylate DA-314,
Denacol Acrylate DA-911 (being Nagase chemteX corporation) etc..
Above-mentioned carbamate (methyl) acrylate for example can be by making isocyanate compound and having hydroxyl
(methyl) acrylic acid derivative reacts in the presence of the tin based compound of catalytic amount to be obtained.
As become above-mentioned carbamate (methyl) acrylate raw material isocyanate compound, it can be mentioned, for example
Isophorone diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI), hexa-methylene diisocyanate
Ester, trimethyl hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate (MDI), hydrogenation MDI, polymerization
MDI, 1,5- naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, two isocyanide of phenylenedimethylidyne
Acid esters (XDI), hydrogenation XDI, lysine diisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyls) are thio
Phosphate, tetramethylxylene diisocyanate, 1,6,11- hendecane triisocyanate etc..
In addition, as above-mentioned isocyanate compound, such as also can be used through ethylene glycol, glycerol, sorbierite, three hydroxyls
The polyalcohols such as methylpropane, (poly-) propylene glycol, carbonate diol, polyetherdiol, polyester-diol, polycaprolactone glycol with it is excessive
Through the isocyanate compound of chain elongation obtained by the reaction of isocyanate compound.
As the raw material for becoming above-mentioned carbamate (methyl) acrylate, (methyl) acrylic acid with hydroxyl spreads out
Biology, it can be mentioned, for example: ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, 1,4-butanediol, polyethylene glycol etc.
List (methyl) acrylate of dihydric alcohol；List (methyl) propylene of the trihydroxylic alcohols such as trimethylolethane, trimethylolpropane, glycerol
Acid esters or two (methyl) acrylate；Bisphenol type epoxy (methyl) acrylate etc. epoxies (methyl) acrylate etc..
As the commercially available product in above-mentioned carbamate (methyl) acrylate, it can be mentioned, for example M-1100, M-1200,
M-1210, M-1600 (being East Asia Synesis Company system), EBECRYL230, EBECRYL270, EBECRYL4858,
EBECRYL8402、EBECRYL8411、EBECRYL8412、EBECRYL8413、EBECRYL8804、EBECRYL8803、
EBECRYL8807、EBECRYL9260、EBECRYL1290、EBECRYL5129、EBECRYL4842、EBECRYL210、
EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220, KRM7735, KRM-8295 (are Daicel-
Allnex corporation), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100,
Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK,
Artresin SH-500B (being Gen Shang industrial group system), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-
6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-
340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-
5201P, UA-7100, UA-7200, UA-W2A (being chemical industrial company of the village Xin Zhong system), AI-600, AH-600,
AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (being chemical company of common prosperity society system) etc..
Other free-radical polymerised compounds other than the above are used alternatively, it is also possible to suitable.
As other above-mentioned free-radical polymerised compounds, it can be mentioned, for example: N, N- dimethyl (methyl) acrylamide,
N- (methyl) acryloyl morpholine, N- hydroxyethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N-
Isopropyl (methyl) acrylamide, N, (methyl) acrylamide compound such as N- dimethylaminopropyl (methyl) acrylamide；
Vinyl compounds such as styrene, α-methylstyrene, n-vinyl pyrrolidone, N- vinyl caprolactam etc..
For the content of above-mentioned free-radical polymerised compound, relative to above-mentioned free-radical polymerised compound with it is above-mentioned
Total 100 parts by weight of wet-cured type polyurethane resin, preferred lower limit is 10 parts by weight, the preferred upper limit is 80 parts by weight.
If the content of above-mentioned free-radical polymerised compound less than 10 parts by weight, makes resulting smooth wet-cured type resin combination sometimes
Composition as photo-curable difference.If the content of above-mentioned free-radical polymerised compound is more than 80 parts by weight, sometimes gained
Light wet-cured type resin combination become moisture curable difference composition.The content of above-mentioned free-radical polymerised compound is more
Preferred lower limit is 25 parts by weight, the preferred upper limit is 70 parts by weight, further preferred lower limit is 30 parts by weight, further
The preferred upper limit is 59 parts by weight.
From viewpoints such as adjustment curability, above-mentioned free-radical polymerised compound preferably comprises monofunctional free radical's polymerization
Property compound and multifunctional free-radical polymerised compound.In the case where monofunctional free radical's polymerizable compound is used only,
Sometimes resulting smooth wet-cured type resin combination becomes the composition of curability difference, multifunctional free-radical polymerised being used only
In the case where compound, sometimes resulting smooth wet-cured type resin combination becomes the composition of viscosity difference.Wherein, more preferably will
As in the molecule of above-mentioned monofunctional free radical's polymerizable compound with nitrogen-atoms compound, with as it is above-mentioned it is multifunctional from
It is applied in combination by carbamate (methyl) acrylate of base polymerizable compound.In addition, above-mentioned multifunctional free radical polymerization
Property compound is preferably 2 functions or 3 functions, more preferably 2 functions.
Contain above-mentioned monofunctional free radical's polymerizable compound and above-mentioned multifunctional in above-mentioned free-radical polymerised compound
In the case where free-radical polymerised compound, for the content of above-mentioned multifunctional free-radical polymerised compound, relative to upper
Total 100 parts by weight of monofunctional free radical's polymerizable compound and above-mentioned multifunctional free-radical polymerised compound are stated, preferably
Lower limit be 2 parts by weight, the preferred upper limit is 45 parts by weight.If the content of above-mentioned multifunctional free-radical polymerised compound is insufficient
2 parts by weight, then sometimes resulting smooth wet-cured type resin combination becomes the composition of curability difference.If above-mentioned multifunctional freedom
The content of base polymerizable compound is more than 45 parts by weight, then sometimes resulting smooth wet-cured type resin combination becomes viscosity difference
Composition.The preferred lower limit of the content of above-mentioned multifunctional free-radical polymerised compound is 5 parts by weight, the preferred upper limit
For 35 parts by weight.
Light wet-cured type resin combination of the invention contains optical free radical polymerization initiator.
As above-mentioned optical free radical polymerization initiator, it can be mentioned, for example benzophenone based compound, acetophenone based compound,
Acylphosphine oxide compound, titanocenes based compound, oxime ester based compound, benzoin ether based compound, thioxanthones etc..
As the commercially available product in above-mentioned optical free radical polymerization initiator, it can be mentioned, for example IRGACURE184,
IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE784、IRGACURE819、IRGACURE907、
IRGACURE2959, IRGACUREOXE01, Lucirin TPO (being BASF Japan corporation), benzoin methylether, benzene are even
Relation by marriage ether, benzoin iso-propylether (being Tokyo chemical conversion industry corporation) etc..
For the content of above-mentioned optical free radical polymerization initiator, relative to above-mentioned 100 weight of free-radical polymerised compound
Part is measured, preferred lower limit is 0.01 parts by weight, the preferred upper limit is 10 parts by weight.If above-mentioned optical free radical polymerization initiator contains
Amount can not then make the resulting smooth abundant photocuring of wet-cured type resin combination less than 0.01 parts by weight sometimes.If above-mentioned light is certainly
It is more than 10 parts by weight by the content of base polymerization initiator, then the storage stability of sometimes resulting smooth wet-cured type resin combination
It reduces.The preferred lower limit of the content of above-mentioned optical free radical polymerization initiator is 0.1 parts by weight, the preferred upper limit is 5 weights
Measure part.
From the viewpoints such as coating, the shape retention for adjusting resulting smooth wet-cured type resin combination, the present invention
Light wet-cured type resin combination can contain filler.
The preferred lower limit of the primary particle size of above-mentioned filler is 1nm, the preferred upper limit is 50nm.If above-mentioned filler
Primary particle size is less than 1nm, then resulting smooth wet-cured type resin combination becomes the composition of coating difference.If above-mentioned filler
Primary particle size be more than 50nm, then resulting smooth wet-cured type resin combination become coating after shape retention difference combination
Object.Under the preferred lower limit of the primary particle size of above-mentioned filler is 5nm, the preferred upper limit is 30nm, is further preferred
It is limited to 10nm, the further preferred upper limit is 20nm.
It should be noted that NICOMP 380ZLS (PARTICLE can be used in the primary particle size of above-mentioned filler
SIZING SYSTEMS corporation) and be distributed to above-mentioned filler in solvent (water, organic solvent etc.) to be measured.
In addition, above-mentioned filler is sometimes in light wet-cured type resin combination of the invention with offspring (multiple one
Secondary particle buildup forms) form exist, the preferred lower limit of the partial size of such offspring is 5nm, the preferred upper limit is
500nm, preferred lower limit are 10nm, the preferred upper limit is 100nm.The partial size of the offspring of above-mentioned filler can lead to
It crosses and observes light wet-cured type resin combination or its solidfied material of the invention using transmission electron microscope (TEM) to be surveyed
It is fixed.
As above-mentioned filler, it can be mentioned, for example silica, talcum, titanium oxide, zinc oxide etc..Wherein, from make gained
Light wet-cured type resin combination become the excellent composition of UV photopermeability in terms of set out, preferred silica.These
Filler may be used singly or in combination of two or more.
It is preferred that implementing hydrophobic surface treatments to above-mentioned filler.By above-mentioned hydrophobic surface treatments, thus resulting
Light wet-cured type resin combination becomes the superior composition of shape retention after coating.
As above-mentioned hydrophobic surface treatments, silylated processing, alkylation processing, epoxidation processing etc. can be enumerated.
Wherein, from the excellent effect aspect for improving shape retention, preferably silylated processing, more preferable trimethyl first silicon
Alkylation processing.
As the method for carrying out hydrophobic surface treatments to above-mentioned filler, it can be mentioned, for example use the tables such as silane coupling agent
The method etc. that surface treatment agent handles the surface of filler.
Specifically, for example, above-mentioned trimethylsilylation processing silica can for example come by the following method
Production: using the methods of sol-gal process synthetic silica, spraying two silicon of hexamethyl in the state of making silica flow
The method of azane；Silica is added into organic solvents such as alcohol, toluene, adds hexamethyldisilazane and water, later, benefit
Make the method etc. of water and organic solvent evaporation drying with evaporator.
For the content of above-mentioned filler, in whole 100 parts by weight of light wet-cured type resin combination of the invention,
Preferred lower limit is 1 parts by weight, the preferred upper limit is 20 parts by weight.If the content of above-mentioned filler is less than 1 parts by weight, sometimes
Resulting smooth wet-cured type resin combination becomes the composition of the shape retention difference after coating.If the content of above-mentioned filler
More than 20 parts by weight, then sometimes resulting smooth wet-cured type resin combination becomes the composition of coating difference.Above-mentioned filler
Content preferred lower limit be 2 parts by weight, the preferred upper limit is 15 parts by weight, further preferred lower limit is 3 weight
Part, the further preferred upper limit are 10 parts by weight, particularly preferred lower limit is 4 parts by weight.
Light wet-cured type resin combination of the invention can contain opacifier.By containing above-mentioned opacifier, thus this
The light wet-cured type resin combination of invention becomes the excellent composition of light-proofness, can prevent the light leakage of display element.
It should be noted that in the present specification, above-mentioned " opacifier " refers to the light being not easy through visible light region
Ability material.
As above-mentioned opacifier, it can be mentioned, for example iron oxide, titanium is black, nigrosine, Cyanine Black, fullerene, carbon black, resin quilt
Cover type carbon black etc..In addition, above-mentioned opacifier can not be the substance in black, it is not easy as long as having through visible light region
The material of the ability of light, then silica, talcum, titanium oxide etc. are also contained in above-mentioned shading as material cited by filler
In agent.Wherein, preferably titanium is black.
Above-mentioned titanium is black be near ultraviolet range, the transmitance of the light of especially 370~450nm of wavelength compare wavelength 300
The high substance of the mean transmissivity of the light of~800nm.That is, above-mentioned titanium is black for the wavelength by sufficiently covering visible light region
Light and assign light-proofness to light wet-cured type resin combination of the invention, on the other hand make wavelength near ultraviolet range
Light penetrate property opacifier.Therefore, got higher by using the transmitance that above-mentioned titanium can be utilized black wavelength (370~
Light 450nm) carrys out the substance of initiation reaction as optical free radical polymerization initiator, so as to further increase light of the invention
The photo-curable of wet-cured type resin combination.Moreover, on the other hand, as light wet-cured type resin combination institute of the invention
The high substance of the opacifier contained, preferably insulating properties, the opacifier high as insulating properties, it is also preferred that titanium is black.
The black optical density of above-mentioned titanium (OD value) is preferably 3 or more, more preferably 4 or more.In addition, the degree of blackness that above-mentioned titanium is black
(L value) is preferably 9 or more, more preferably 11 or more.The higher the better for the black light-proofness of above-mentioned titanium, and the black OD value of above-mentioned titanium has no spy
The not preferred upper limit, but usually 5 or less.
For above-mentioned titanium is black, even the titanium without surface treatment is black, sufficient effect can be also played, but can also
To use surface to be coupled, the processed titanium of the organic principles such as agent is black, is oxidized silicon, titanium oxide, germanium oxide, aluminium oxide, oxidation
The surface treated titaniums such as the coating titanium of the inorganic constituents such as zirconium, magnesia is black are black.Wherein, from insulating properties can be further increased
Aspect set out, it is preferably black by the processed titanium of organic principle.
In addition, for the display element manufactured using light wet-cured type resin combination of the invention, since light is wet solid
Change type resin combination has sufficient light-proofness, therefore becomes unglazed leakage, with high contrast and with excellent figure
As the display element of display quality.
As above-mentioned titanium it is black in commercially available product, it can be mentioned, for example 12S, 13M, 13M-C, 13R-N (be Mitsubishi Materials public affairs
Department's system), Tilack D (red fringe chemical conversion corporation) etc..
The preferred lower limit of the black specific surface area of above-mentioned titanium is 5m2/ g, the preferred upper limit are 40m2/ g, preferred lower limit
For 10m2/ g, the preferred upper limit are 25m2/g。
In addition, the preferred lower limit of the black sheet resistance of above-mentioned titanium is under (70% cooperation) the case where mixing with resin
109Ω/, preferred lower limit are 1011Ω/□。
In light wet-cured type resin combination of the invention, the primary particle size of above-mentioned opacifier selects depending on the application and suitably
The distance being selected as between the substrate of display element is such as the following, and preferred lower limit is 30nm, the preferred upper limit is 500nm.If above-mentioned screening
The primary particle size of photo etching is less than 30nm, then viscosity, the thixotropy of sometimes resulting smooth wet-cured type resin combination substantially increase,
Operability is deteriorated.If the primary particle size of above-mentioned opacifier is more than 500nm, in sometimes resulting smooth wet-cured type resin combination
Opacifier dispersibility reduce, light-proofness reduce.The preferred lower limit of the primary particle size of above-mentioned opacifier is 50nm, more excellent
The upper limit of choosing is 200nm.
It should be noted that NICOMP 380ZLS (PARTICLE SIZING can be used in the partial size of above-mentioned opacifier
SYSTEMS corporation) and be distributed to above-mentioned opacifier in solvent (water, organic solvent etc.) to acquire average grain diameter to be surveyed
It is fixed.
The content of above-mentioned opacifier in light wet-cured type resin combination entirety of the invention is not particularly limited, preferably
Lower limit be 0.05 weight %, the preferred upper limit is 10 weight %.If the content of above-mentioned opacifier has less than 0.05 weight %
When be unable to get sufficient light-proofness.If the content of above-mentioned opacifier is more than 10 weight %, sometimes resulting smooth wet-cured type
Resin combination is to the strength reduction after the cementability of substrate etc., solidification, or makes the reduction of drawing property.The content of above-mentioned opacifier
Preferred lower limit be 0.1 weight %, the preferred upper limit is 2 weight %, the further preferred upper limit is 1 weight %.
Light wet-cured type resin combination of the invention, which can according to need, further contains colorant, ionic liquid, molten
Agent contains the additives such as metallic, reactive diluent.
As the method for manufacturing light wet-cured type resin combination of the invention, it can be mentioned, for example use homogenous disperse machine,
The mixing machines such as homogeneous mixer, universal mixer, planetary-type mixer, kneader, 3 roller machines by free-radical polymerised compound,
Wet-cured type polyurethane resin, optical free radical polymerization initiator and the method for additive mixing being added as needed etc..
Light wet-cured type resin combination of the invention, using cone plate type viscometer surveyed under conditions of 25 DEG C, 1rpm
The preferred lower limit of fixed viscosity is 50Pas, the preferred upper limit is 500Pas.If above-mentioned viscosity is less than 50Pas or super
500Pas is crossed, then light wet-cured type resin combination is being used for electronic component-use bonding agent, display element bonding agent
In the case of, operability when being coated on the adherends such as substrate sometimes is deteriorated.The preferred lower limit of above-mentioned viscosity be 80Pas,
The preferred upper limit is 300Pas, the further preferred upper limit is 200Pas.
The preferred lower limit of the thixotropic index of light wet-cured type resin combination of the invention is 1.3, the preferred upper limit is
5.0.If above-mentioned thixotropic index less than 1.3 or more than 5.0, is glued light wet-cured type resin combination is used for electronic component-use
In the case where connecing agent or display element bonding agent, operability when being coated on the adherends such as substrate sometimes is deteriorated.Above-mentioned thixotroping
The preferred lower limit of index is 1.5, the preferred upper limit is 4.0.
It should be noted that the above-mentioned thixotropic index in this specification refers to: using cone plate type viscometer in 25 DEG C, 1rpm
Under conditions of the viscosity that measures divided by the resulting value of viscosity for using cone plate type viscometer to measure under conditions of 25 DEG C, 10rpm.
About light wet-cured type resin combination of the invention, solidfied material 25 DEG C of tensile modulus of elasticity it is preferred under
It is limited to 0.5kgf/cm2, the preferred upper limit be 6kgf/cm2.If above-mentioned tensile modulus of elasticity is less than 0.5kgf/cm2, then mistake sometimes
In softness, and cohesiveness is weak, and bonding force is lower.If above-mentioned tensile modulus of elasticity is more than 6kgf/cm2, then flexibility is damaged sometimes.
The preferred lower limit of above-mentioned tensile modulus of elasticity is 1kgf/cm2, the preferred upper limit be 4kgf/cm2。
It should be noted that above-mentioned " tensile modulus of elasticity " in this specification refers to using cupping machine (such as island
Saliva manufacturing company system, " EZ-Graph ") solidfied material is stretched with the speed of 10mm/min and when being stretched to 50%
Power form measurement value.
Light wet-cured type resin combination of the invention can especially be suitable as electronic component-use bonding agent, display element
Use bonding agent.Using electronic component-use bonding agent made of light wet-cured type resin combination of the invention and using of the invention
The bonding agent of display element made of light wet-cured type resin combination is also respectively one of present invention.
Invention effect
According to the present invention it is possible to provide the light wet-cured type resin excellent in reliability under cementability and hot and humid environment
Composition.In addition, it is also possible according to the present invention to provide viscous using electronic component-use made of the light wet-cured type resin combination
Connect agent and display element bonding agent.
Detailed description of the invention
Fig. 1 (a) is schematic diagram the case where indicating cementability sample for evaluation viewed from above, and Fig. 1 (b) is to indicate from cross
To schematic diagram the case where observing cementability sample for evaluation.
Specific embodiment
Hereinafter, enumerating embodiment, the present invention will be described in more detail, and still, the present invention not shall be limited only to the extent these realities
Apply example.
(synthesis example 1 (production of carbamate prepolymer A))
By as the polytetramethylene ether diol of 100 parts by weight of polyol compound (Mitsubishi Chemical Ind's system,
" PTMG-2000 ") and the dibutyl tin dilaurate of 0.01 parts by weight be put into the removable flask of capacity 500mL, in vacuum
Under (20mmHg or less) in 100 DEG C stir 30 minutes, mixed.Later, it is set as normal pressure, is added and is used as polyisocyanate chemical combination
Methyl diphenylene diisocyanate (Cao Itochu system, " Pure MDI ") 26.5 parts by weight of object are small in 80 DEG C of stirrings 3
When, make its reaction, obtains carbamate prepolymer A (weight average molecular weight 2700).
(synthesis example 2 (production of carbamate prepolymer B))
It will be as the polypropylene glycol of 100 parts by weight of polyol compound (Asahi Glass corporation, " EXCENOL 2020 ")
Be put into the removable flask of capacity 500mL with the dibutyl tin dilaurate of 0.01 parts by weight, under vacuum (20mmHg with
Under) stirred 30 minutes in 100 DEG C, it is mixed.Later, it is set as normal pressure, the diphenyl as polyisocyanate compounds is added
Methane diisocyanate (Cao Itochu system, " Pure MDI ") 26.5 parts by weight stir 3 hours at 80 DEG C, make its reaction,
Obtain carbamate prepolymer B (weight average molecular weight 2900).
(synthesis example 3 (production of carbamate prepolymer C))
Be put into operated in the same way with synthesis example 1 obtained from carbamate prepolymer A 100 parts by weight react
1.3 parts by weight of hydroxyethyl methacrylate and N- nitroso phenyl hydroxylamine aluminium salt (and the light as polymerization inhibitor are added in container
Chun Yao industrial group system, " Q-1301 ") 0.14 parts by weight, it is stirred 1 hour under stream of nitrogen gas in 80 DEG C, obtains dividing
Sub- end has the carbamate prepolymer C (weight average molecular weight 2900) of isocyanate group and methylacryloyl.
(synthesis example 4 (production of carbamate prepolymer D))
Be put into operated in the same way with synthesis example 1 obtained from carbamate prepolymer A 100 parts by weight react
3-mercaptopropyi trimethoxy silane (chemical industrial company of SHIN-ETSU HANTOTAI system, " KBM-803 ") 9.8 parts by weight are added in container,
80 DEG C are stirred 1 hour, obtain it is as the polyurethane resin containing Organosilyl, molecular end have isocyanates
The carbamate prepolymer D (weight average molecular weight 3100) of base and trimethoxysilyl.
(embodiment 1~15, Comparative Examples 1 and 2)
According to the match ratio recorded in table 1,2, by the planetary agitating device of each material use (Thinky corporation, " あ わ
と り practice Taro ") be stirred after, equably mixed using ceramic three-roller, obtain the light of embodiment 1~15, Comparative Examples 1 and 2
Wet-cured type resin combination.
It should be noted that " the carbamate prepolymer A " in table 1,2 is to be recorded in synthesis example 1 in two ends tool
There is the carbamate prepolymer of isocyanate group, " carbamate prepolymer B " is to be recorded in synthesis example 2 in two ends tool
There is the carbamate prepolymer of isocyanate group, " carbamate prepolymer C " is to be recorded in synthesis example 3 in molecular end
Carbamate prepolymer with isocyanate group and methylacryloyl, " carbamate prepolymer D " are in synthesis example 4
Middle record has the carbamate prepolymer of isocyanate group and trimethoxysilyl in molecular end.
< evaluates >
Evaluation below has been carried out to each smooth wet-cured type resin combination obtained in Examples and Comparative Examples.By result
It is shown in table 1, in 2.
It should be noted that being bonded the time in substrate for the light wet-cured type resin combination obtained in the comparative example 2
Wet-cured type resin combination is crushed, and can not make the sample in each evaluation, therefore can not conduct the following evaluation.
(cementability)
Using each obtained in width coating Examples and comparative example of the dispersal device on polycarbonate substrate with about 2mm
Light wet-cured type resin combination.Later, using UV-LED (wavelength 365nm), with 1000mJ/cm2Ultraviolet light is irradiated, thus
Make light wet-cured type resin combination photocuring.Later, glass plate is bonded with polycarbonate substrate, places the weight of 20g, and
A night is placed, its moisturecuring is made, obtains cementability sample for evaluation.It is shown in Fig. 1: indicating that cementability evaluation viewed from above is used
Schematic diagram (the Fig. 1 of the schematic diagram (Fig. 1 (a)) and expression of the case where sample from laterally the case where cementability sample for evaluation
(b))。
Using cupping machine (Shimadzu Seisakusho Ltd.'s corporation, " Ez-Grapf "), by made cementability evaluation sample
Product are stretched along shear direction with the speed of 5mm/sec, intensity when measurement polycarbonate substrate and glass plate are removed.
(high temperature and humidity reliability (creep resistant))
High temperature and humidity reliability is made in the same manner as the cementability sample for evaluation in the evaluation of above-mentioned " (cementability) " to comment
Valence sample.Resulting high temperature and humidity reliability evaluation is vertically hung with sample relative to ground, in polycarbonate base
The state that the end of plate hangs with the weight of 120g is put into the constant temperature constant humidity baking oven of 60 DEG C of 95%RH, stands 24 hours.It stands
After 24 hours, polycarbonate substrate and the unstripped situation of glass plate are evaluated as "○", by polycarbonate substrate and glass plate
The case where the case where being partially stripped is evaluated as " △ ", polycarbonate substrate and glass plate are completely exfoliated is evaluated as "×", thus
The high temperature and humidity reliability (creep resistant) of light wet-cured type resin combination is evaluated.
(flexibility)
Using high-pressure sodium lamp, with 1000mJ/cm2Ultraviolet light is irradiated, each light obtained in Examples and Comparative Examples is thus made
Wet-cured type resin combination photocuring places a night, makes its moisturecuring later.Resulting solidfied material is punched as dumbbell shaped
(No. 6 shapes specified in " JIS K 6251 ") and obtain test film, by the coupons use cupping machine (Shimadzu Seisakusho Ltd.
Corporation, " EZ-Graph ") it is stretched with the speed of 10mm/min, power when being stretched to 50% is acquired as elasticity modulus.
Industrial availability
According to the present invention it is possible to provide the light wet-cured type resin excellent in reliability under cementability and hot and humid environment
Composition.In addition, being bonded according to the present invention it is possible to provide using electronic component-use made of the light wet-cured type resin combination
Agent and display element bonding agent.
Symbol description
1 polycarbonate substrate
2 smooth wet-cured type resin combinations
3 glass plates
Claims (8)
1. a kind of smooth wet-cured type resin combination, which is characterized in that contain free-radical polymerised compound, the poly- ammonia of wet-cured type
Ester resin and optical free radical polymerization initiator,
The wet-cured type polyurethane resin contains with group and isocyanates shown in urethane bond, following formula (1)
The compound of base,
—Si(R′)x(OR2)3-x (1)
In formula (1), R1And R2For hydrogen, the alkyl or aryl of carbon number 1~5, R1And R2Can be identical or different respectively, x is 0~2,
The content with group shown in urethane bond, formula (1) and the compound of isocyanate group is relative to described
Total 100 parts by weight of free-radical polymerised compound and the wet-cured type polyurethane resin are 2 parts by weight or more and 50 weights
Measure part hereinafter,
The content of the wet-cured type polyurethane resin is poly- relative to the free-radical polymerised compound and the wet-cured type
Total 100 parts by weight of urethane resin are 41 parts by weight or more and 90 parts by weight or less.
2. smooth wet-cured type resin combination according to claim 1, which is characterized in that also containing except with carbamic acid
Group shown in ester bond, formula (1) and other wet-cured type polyurethane resins other than the compound of isocyanate group.
3. smooth wet-cured type resin combination according to claim 1 or 2, which is characterized in that free-radical polymerised chemical combination
Object contains monofunctional free radical's polymerizable compound and multifunctional free-radical polymerised compound.
4. smooth wet-cured type resin combination according to claim 3, which is characterized in that multifunctional free-radical polymerisedization
Close total 100 weights of the content of object relative to monofunctional free radical's polymerizable compound and multifunctional free-radical polymerised compound
Amount part is 2~45 parts by weight.
5. smooth wet-cured type resin combination according to claim 1 or 2, which is characterized in that containing primary particle size be 1~
The filler of 50nm.
6. smooth wet-cured type resin combination according to claim 1 or 2, which is characterized in that contain opacifier.
7. a kind of electronic component-use bonding agent, which is characterized in that be wet solid using light described in claim 1,2,3,4,5 or 6
Made of change type resin combination.
8. a kind of display element bonding agent, which is characterized in that be wet solid using light described in claim 1,2,3,4,5 or 6
Made of change type resin combination.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910013933.7A CN109679031A (en) | 2014-05-13 | 2015-05-11 | Light wet-cured type resin combination, electronic component-use bonding agent and display element bonding agent |
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| JP2014099743 | 2014-05-13 | ||
| JP2014-099743 | 2014-05-13 | ||
| PCT/JP2015/063484 WO2015174371A1 (en) | 2014-05-13 | 2015-05-11 | Photo- and moisture-curing resin composition, adhesive for electronic parts, and adhesive for display element |
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| CN201910013933.7A Division CN109679031A (en) | 2014-05-13 | 2015-05-11 | Light wet-cured type resin combination, electronic component-use bonding agent and display element bonding agent |
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| CN201910013933.7A Pending CN109679031A (en) | 2014-05-13 | 2015-05-11 | Light wet-cured type resin combination, electronic component-use bonding agent and display element bonding agent |
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| KR (1) | KR102320903B1 (en) |
| CN (2) | CN105814094B (en) |
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| CN107075061B (en) * | 2015-04-09 | 2021-08-24 | 积水化学工业株式会社 | Light-moisture-curable resin composition, adhesive for electronic component, and adhesive for display element |
| TWI701310B (en) * | 2015-04-17 | 2020-08-11 | 日商積水化學工業股份有限公司 | Hardened bodies, electronic parts, display elements, and light and moisture hardening resin compositions |
| KR102653979B1 (en) * | 2015-12-02 | 2024-04-02 | 세키스이가가쿠 고교가부시키가이샤 | Light/moisture curable resin composition, adhesive agent for electronic parts, and adhesive agent for display elements |
| JP6878289B2 (en) * | 2016-08-09 | 2021-05-26 | 積水化学工業株式会社 | Adhesive compositions, cured products, electronic components and assembly components |
| KR102458390B1 (en) * | 2016-11-14 | 2022-10-24 | 세키스이가가쿠 고교가부시키가이샤 | Moisture-curable resin composition and assembly parts |
| CN110832034B (en) * | 2017-08-18 | 2022-10-18 | 积水化学工业株式会社 | Moisture-curable resin composition, adhesive for electronic component, and adhesive for display element |
| JP7228088B2 (en) * | 2018-10-09 | 2023-02-24 | Dic株式会社 | Resin composition and article formed from said resin composition |
| JP7205149B2 (en) * | 2018-10-09 | 2023-01-17 | Dic株式会社 | Resin composition and article formed from said resin composition |
| CN116568760B (en) * | 2020-11-30 | 2024-10-29 | 积水化学工业株式会社 | Moisture-curable resin composition and adhesive for electronic device |
| CN115353810B (en) * | 2022-09-08 | 2024-01-30 | 杭州之江有机硅化工有限公司 | UV and moisture dual-curing adhesive as well as preparation method and application thereof |
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- 2015-05-11 CN CN201910013933.7A patent/CN109679031A/en active Pending
- 2015-05-11 KR KR1020167007877A patent/KR102320903B1/en active Active
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- 2015-05-11 WO PCT/JP2015/063484 patent/WO2015174371A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2016065247A (en) | 2016-04-28 |
| TWI670326B (en) | 2019-09-01 |
| TW201600558A (en) | 2016-01-01 |
| CN105814094A (en) | 2016-07-27 |
| WO2015174371A1 (en) | 2015-11-19 |
| CN109679031A (en) | 2019-04-26 |
| KR20170008714A (en) | 2017-01-24 |
| KR102320903B1 (en) | 2021-11-02 |
| JP5844504B1 (en) | 2016-01-20 |
| JPWO2015174371A1 (en) | 2017-04-20 |
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